Novel laundering compositions

ABSTRACT

A new liquid detergent system is disclosed wherein a compound of the formula:   IS EMPLOYED AS A BACTERIOSTAT. A novel method of solubilizing this bacteriostat in the liquid detergent system is also disclosed.

United States Patent Corey et al. 5] Dec. 9, 1975 NOVEL LAUNDERINGCOMPOSITIONS 3,700,601 10/1972 Bloching 252/105 1 Inventors: Garland 9y, Milltown; FOREIGN PATENTS 0R APPLICATIONS 'P Weinstein, North1,526,645 4/1968 France Plamfield, bOth of 990,696 4/1965 United Kingdom{731 Assignee: American Home Products 1'226338 3/197 Ummd KmgdomCorporation, New o k, NY. OTHER PUBLICATIONS 1 1 Filfidi p 1973 TheMiranol Sulfonated Surface Active Agents, The {21] AppL NOJ 401,736{\i/lnir(aln;3C)hem. C0., lnc., New Jersey, Product Bulle- Related [1.8.Application Data [63] Continuation-impart of Ser. No. 258,153, May 3],Primary Examiner-P. E. Willis, Jr.

1972, abandoned. Attorney, Agent, or Firm-Stephen Venetianer [52] US.Cl. 252/106; 252/545; 252/546;

252/547; 252/548; 252/551; 252/553; 252/558 [57] ABSIRACT [51} Int. Cl.Cl 1D 3/48; Cl 1D 3/29 A new liquid detergent system is disclosedwherein a [58] Field of Search 252/106, 107, 551, 553, compound of theformula:

[56] References Cited Cl 0 l UNITED STATES PATENTS 3,303,138 2/1967Dewitt et al. 252/546 X 01 H 3,440,319 4/1969 Wilson 1 1 424/2303,501,409 3/1970 Matson et al. 252/551 3,503,885 3/1970 Wedell 252/105is employed as a bacteriostat. A novel method of solu- 3.5 3.099 5/1970Hans et a1 252/551 X bilizing this bacteriostat in the liquid detergentsystem 3,533,955 10/1970 Pader et al 252/153 is also disclosecL3,538,217 ll/l970 Dewar et al. 424/173 3,594,322 7/l971 Wilson 252/l06 3Claims, N0 Drawings NOVEL LAUNDERING COMPOSITIONS This application is acontinuation-in-part of Ser. No. 258,153 filed May 31, 1972, nowabandoned.

BACKGROUND OF THE INVENTION 1. Field of the Invention This inventionrelates to a novel liquid detergent system that exhibits bacteriostaticaction. More particularly, it relates to such a system that contains2,4,4'-trichloro-2'-hydroxy-diphenyl ether as an active bacteriostat.Additionally, this invention deals with a unique method for solubilizingthe above bacteriostat in a liquid detergent system.

2. Description of the Prior Art 1 It has long been known that it isdesirable to include some type of bacteriostat in detergents and soapsto prevent bacteria growth and to sanitize fabrics. Over the years therehave appeared numerous commercial products that have been somewhateffective in controlling the growth of undesirable bacteria. Theseproducts usually fall into three categories, namely, hexachlorophene,halogenated carbanilides and tribromosalicylaand their use asbactericidals. This patent discloses that a preferred use for thesecompounds is in disinfecting goods which are washed and in protectingthese goods from attack by microorganisms. US. Pat. No. 3,506,720primarily deals with the use of these patented ether compounds inlaundering solutions in which the halogenated hydroxy-diphenyl ethersexist in solution as phenolic salts in a basic medium.

SUMMARY OF THE INVENTION It is therefore one of the objects of thisinvention to provide a liquid detergent system in which the activebacteriostat, namely, 2,4,4-trichloro-2-hydroxydiphenyl ether exists asa phenol in solution. This is accomplished by solubilizing the abovecompound with a solution of sodium lauryl ether sulfate. The resultingliquid detergent system has a pH of about 7-8 which consequentlyproduces a liquid detergent system having superior bacteriostaticproperties.

DESCRIPTION OF PREFERRED EMBODIMENTS The liquid detergent system of thisinvention consists essentially of the following components:

% By Weight 1, Triethanolamine linear dodecyl benzene 0,1 50% sulfonate(40% active in an aqueous solution) 2. Sodium lauryl ether sulfate (57%active 01 20% in 18% ethanol and the remainder water) 3. Dirnethylcocoamine oxide (40% active in water] 0.1 2% 4. Am photeric coconut acidderivative having the following formula:

N CH II I) R-C N Formula I. I CH CHCH SO M OH OH wherein R is a mixtureof hydrocarbon radicals ranging from about 10 to about 18 carbon atomsand M is hydrogen or an alkali metal. 01 4% 5. Coconut fatty aciddiethanolamine condensate 0.1 2% 6. 2,4,4'-trichloro'2-hydroxydiphenylether 0.10 1.00% 7. Ethanol 0.1 1071 8. Water Sufficient quantity tomake to 100% nide. Addtionally, quaternary ammonium germicidal agents ormicrobiologically active ingredients based on phenolic derivatives havebeen employed for the above purpose.

Recently, US. Pat. No. 3,506,720 issued Apr. 14, 1970 disclosinghalogenated hydroxy-diphenyl ethers In addition the above liquiddetergent system may con- 50 tain the usual additives such as opticalbrighteners, perfumes and antiredeposition agents.

A preferred range for the above components is as follows:

The above liquid detergent system has the ability to reduce clothes odorthat is brought about by bacterial degradation after the garment hasbeen washed or during wear. The system has the ability to deposit theactive anti-bacterial agent onto a fabric during a washing operation foreffective deodorant activity.

A preferred method of preparation is to solubilize the2,4,4'-trichloro-2'-hydroxydiphenyl ether with sodium lauryl ethersulfate seperately and then to add this so called pre-mix solution tothe other components of the novel laundering composition of thisapplication.

4 min. wash time. Cloth Load U.S. Testing 4 X 8 inch cloths Type 2Cotton, 2 Spun Nylon, 3 Dacron/Cotton,

2 W001 Flannel. Total weight of cloth per bucket about 22.5g. Afterrinsing and drying, the cloth swatches were subjected to testing forbacteriostatic activity via the Agar Plate Test (USDA Circular No. 198;1931). The following zones of inhibition" were observed against S.aureus and E. coli.

Complete solubility of the pre-mix solution is indicated Ta ll when thepre-mix solution is substantially clear. The pH Zones of InhibitionComposition of Exampe of the pre-mix solution after solubihzatlon rangesfrom (mm) on s. aureus about 8.4 to 8.7. A B C D E F G Triethanolaminelinear dodecyl benzene sulfonate Cotton 29 19 29 28 2s 25 19 (4O% act1ve In an aqueous solutlonl is added in a vesalig A? 53 i sel, distinctfrom the pre-mlx solution, to water with wool 15 12 M 3 2| moderateagitation. Optical brightners or other optional compounds may be addedat this point. The premix solution which contains2,4,4'-trichloro-2'-hydroxydiphenyl ether solubilized in sodium laurylether sulable fate is then added accompanied by agitation and the re-Zones of Inhibition Com position of Example I maining ingredients of thecomposition are then added. (mm) of This method of preparation providesfor the solubility A B C D E F G of the bacteriostatic component and isthe method em- Cotton 23 11 26 17 14 17 24 ployed in the preparation ofthe composition illustrated ggzg 2 3 g i; in Example 1. This method alsoprovides a liquid deterw 6 5 6 3 7 4 5 gent composition that hassuperior stability properties.

The following Examples further illustrate this inven- 30 EXAMPLE 3EXAMPLE l The composition of Example la was utilized to wash ThisExample illustrates the preparation of the laungarments that were firstworn and then washed accorddering composition of this application. Italso illustrates ing to the following procedures: the necessity ofemploying sodium lauryl ether sulfate Hand Laundering 26 cc. of liquiddetergent from to keep 2,4,4'-trichloro-2'-hydroxyphenyl ether in so-Example 1 was diluted into 1 gallon of water and lution. the garmentswere taken utilizing a Hunter D-25 Table I BY WElGHT Components A B C DE F G Water 499 81.9 56.4 50.0 51.5 50.9 51.9 Triethanolamine lineardodecyl benzene sulfonate (40% active in an aqueous solution) 32.0 32.032.0 32.0 32.0 32.0 Sodium lauryl ether sulfate (57% active in l8%ethanol and the remainder water) 12.5 12.5 12.5 12.5 [2.5 l2.5 Opticalbrightner 0.! 0.1 0.1 0.1 0.1 0.1 Dimethyl coco-amine oxide (40% activein water) 1.6 1.6 1.6 1.6 1.6 1.6 2AA'-trichloro-2'-hydroxydiphenylether 97% minimum activity) 0.7 0.7 0.7 0.7 0.7 0.7 0.7 Coconut fattyacid diethanolamine condensate 1.0 1.0 L0 1.0 1.0 l.0 Formula I whereinM is sodium 2.0 2.0 2.0 2.0 2.0 2.0 Perfume 0.2 0.2 0.2 0.2 0.2 0.2 0.2SDA 40 ethanol 6.0

Necessary to obtain solubility of the active antibacterial agent.

EXAMPLE 2 60 Reflectometer (L scale) to ascertain cleaning re-Compositions A-G, in Example 1 were used to test lm residualbacteriostatic activity on various types Of Machine Washing 12 lg. ofthe composition as cloths as described below. shown in Example 1 per 16gallons of water in an Terg-O-Tometer tests runs were made under thefolautomatic washer. Reflectometer readings were taken as describedabove.

lowing conditions:

2g/l000 ml use concentration of composition. F water temperature. rpm.

Table IV summarizes the results obtained. Anti-bacterial activity of thegarments washes was measured as in Example 2. Table V summarizes theresults obtained.

Table IV Hunter D-25 Reflectometer Readings (whiteness) Original Unitsof Unsoilcd Soiled Washed Difference Hand Laundering Nylon Slip 70F 95.695.2 95.4 0.2 Nylon Slip 90F 95.8 95.6 95.7 0.1 Nylon Slip l20F 94.494.2 94.3 0.1 Permanent Press Shirt 70F 93.5 90.2 92.2 2.0 PermanentPress Shirt 90F 92.7 91.2 93.2 2.0 Permanent Press Shirt l20F 93.2 91.192.6 1.5 Polyester Blouse 70F 94.1 92.2 93.5 1.3 Cotton Tshirt 70F 96.793.0 96.0 3.0 Wool/Nylon Socks 70F No.1 86.2 82.8 85.0 2.2 No.2 85.984.6 85.1 0.5

Machine Wash i Mixed Load 70F Nylon Slip 95.2 95.l 95.6 0.5 PermanentPress Shin 92.8 89.7 91.5 1.8 Polyester Blouse 94.0 92.2 92.8 0.6 CottonTshirt 96.9 93.9 95.5 1.6 Wool/Nylon Socks No.3 82.5 81.9 82.2 03 No.483.8 82.7 83.2 0.5

TABLE V AVERAGE ZONE OF INHIBITION (mm) (H Hand Washed, M MachineWashed) Garment Weight (01.) S. epidermidis S. aureus E. C h

Wool Sweater H 70F 12 4 l3 7 Polyester Blouse, H 70F 5 l1 l7 9 NylonSlip, H 70F 3 6 3* 1.5" Cotton T-shirt, H 70F 4 l9 19 llPolyester/Cotton Shirt, H 70F 7 11 Wool Sweater, M 70F 12 5 2.5 Cotton'T-shirt, M 70F 4 6 4 Acetate Panties, M 70F 2 3" 2' Polyester Blouse, M70F 5 6 2.5 Nylon Slip, M 70F 3 9 3 Wool/Nylon Socks, M 70F 4 13 8Polyester/Cotton Shirt, M 70F 7 ll 9 Nylon Slip, H 90F 3 4.5 3 NylonSlip, H l20F 3 7 3 Polyester/Cotton Shirt. H l20F 7 21 9Polyester/Cotton Shirt, H 90 7 l9 1 1 Clear zone surrounding the fabricwith very slight areas of growth NOTE:

Garments which were hand washed were done separately.

Machine washing consisted of a three (3) pound load of mixed garments.Wool sweaters were washed separately by hand and by machine.

EXAMPLE 4 TABLE VI-contmued Bacteriostatic studies were conducted on aliquid system similar to Example 1 with the exception that the Example 4Pans of Composition formulation contained tetrapotassium pyrophosphate Bc and no perfume. Standard zones of inhibition were con- Solution)ducted as in Example 2. Table VI illustrates these com- Formula Iwherein M is sodium 200 2.00 2.00 2,00

i e resul Optical brightner 0.10 0.10 0.10 0.10 positions Table VIIllustrates th t 5 wan" 4H0 4H o 4710 47' m TABLE V]2,4,4'-trichloro-2'-hydroxydiphenyl ether (97% minimum Examph 4Compositions activity) 0.00 0.10 0.23 0.50

Parts of Composition A B C Triethanolamine linear 60 What IS claimed is;dodecyl benzene sulfonate (40% active in an aqueous 1. A liquiddetergent formulation which comprises solution) 32.00 32.00 32.00 32.00the following components: Sodium lauryl ether sulfate (57% active in 18%ethanol and the remainder water) 12.50 12.50 12.50 12.50 Triethanolaminelinear dodecyl benzene sulfonate Dimethyl cocoamine oxide 0.1 50% (40%active in water) 1.60 1.60 1.60 1.60 Sodium lauryl ether sulfate 01 20%Coconut. fatty acid diethanolwherein the number of ethoxy groups isthree amine condensate 1.00 1.00 1.00 1.00 Dimethyl cocoamine oxide 012% Perfume 0.10 0.10 0.10 0.10 Tetrapotassium pyrophosphate 3.00 3.003.00 3.00

3,925,227 7 8 Amphoteric coconut acid derivative having the folfate andwherein the pH of the system is about 7 to lowing formula: about 8.

2. A liquid detergent system according to claim 1 wherein the componentshave the following ratios ac- CH 5 cording to their percent by weight: NCH, ll l CZHOH By Welght R C Triethanolamine linear dodecyl benzeneCHICH CHISOBM sulfonate (40% active in an aqueous 30 35 10 solution)Sodium lauryl ether (3 moles ethylene oxide) sulfate (57% active in l8%ethanol wherein R is a mixture of hydrocarbon and the remainder water]It) l5 radicals ranging from about to about Pirnethyl cocoamine oxide(40% active L40 1.80 l8 carbon atoms and M is hydrogen or m i an l limelal 0! 4% Amphoteric coconut acid derivative 1 3 Coconut fatty aciddielhanoaminc 5 Coconut fatty acid diethanolamine condensate 0.5 l.5condensaw 0" 2% 2.4,4'-tricl1loro-2-hydroxydiphenyl ether2.4.4'-trichloro-2'-hydroxydiphenyl ether 0. 104.00%

Water Sufficlent Ethanol quantity to Water Sufficient make to 10%quantity to make to l00% 2O 3. A liquid detergent system according toclaim 1 wherein wherein M of the amphoteric coconut acid derivative is2,4,4'-Trichloro-2'-hydroxydiphenyl ether is prean alkali metal.

mixed and solubilized with sodium lauryl ether sul-

1. A LIQUID DETERGENT FORMULATION WHICH COMPRISES THE FOLLOWINGCOMPONENTS: TRIETHANOLAMINE LINEAR DODECYL BENZENE SULFONATE 0.1 - 50%SODIUM LAURYL ETHER SULFATE 0.1 - 20% WHEREIN THE NUMBER OF ETHOXYGROUPS IS THREE DIMETHYL COCOAMINE OXIDE 0.1 - 2% AMPHOTERIC COCONUTACID DERIVATIVE HAVING THE FOLLOWING FORMULA:
 2. A liquid detergentsystem according to claim 1 wherein the components have the followingratios according to their percent by weight:
 3. A liquid detergentsystem according to claim 1 wherein M of the amphoteric coconut acidderivative is an alkali metal.